Part XVII of "Constituents of Domestic Citrus Plants." The Structures of Neoacrimarines-C and -D, Two New Acridone-Coumarin Dimers from Citrus hassaku.

Chemical and Pharmaceutical Bulletin
1993.0

Abstract

In our phytochemical studies of Citrus plants (Rutaceae), we have isolated many kinds of coumarins, acridone alkaloids, and flavanones. In particular, many acridone-coumarin dimers, named acrimarines, which are constructed from various acridone alkaloids and suberosin as a coumarin unit, are characteristic constituents. We recently reported the isolation and structural elucidation of two novel type acridone-coumarin dimers, named neoacrimarines-A and -B, which contain coumarin units other than suberosin. In further investigations of the constituents of Citrus plants, we isolated two novel neoacrimarines, namely neoacrimarine-C(1) and neoacrimarine-D(2), from the root of Citrus hassaku HORT. ex. TANAKA. Their structures were elucidated on the basis of spectroscopic data including high-resolution fast atom bombardment mass spectrum, 1H- and 13C-NMR, UV, IR, 1H-1H correlation spectroscopy, 1H-13C COSY, heteronuclear multiple-bond connectivity spectroscopy, nuclear Overhauser effect experiments, and chemical derivatization (preparation of mono-methyl ether with diazomethane and diacetate with acetic anhydride–pyridine). Neoacrimarine-C (1) is a dimer of citracridone-III and khellactone with an ether linkage between C-5 of the acridone moiety and C-11' of the coumarin moiety, and its relative stereochemistry of the hydroxyl group (C-10) and ether linkage (C-11') was determined to be cis. Neoacrimarine-D (2) has a linkage between C-2 of the acridone moiety and C-11' of the coumarin moiety, with the linear orientation of the 2,2-dimethylpyran ring in the coumarin moiety established by HMBC experiment.

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